A modified four-state model for the "dual fluorescence" of N(6),N(6)-dimethyladenine derived from femtosecond fluorescence spectroscopy.

The radiationless deactivation of the excited electronic states of the dual fluorescence molecule N(6),N(6)-dimethyladenine (DMAde) was investigated using femtosecond time-resolved fluorescence up-conversion spectroscopy. The molecules were studied in solution in water and in dioxane. Fluorescence-time profiles were recorded in the wide wavelength range of 290 electronic origin (lambda(pump) = 294 nm) to excess energies of approximately 5400 cm(-1) above (lambda(pump) = 258 nm). Global fits to the measured curves turned out to reflect distinctive molecular relaxation processes on five well-defined time scales. Sub-100 fs and 0.52(3) ps lifetimes were found to predominate at the shortest UV and blue emission wavelengths in water, 1.5(1) and 3.0(2) ps components at intermediate wavelengths and a 62(1) ps value in the red region of the spectrum (2sigma error limits of the last digits in parentheses). In dioxane, these lifetimes changed to parent molecule adenine (Ade), the observations were rationalized with the help of a modified four-state model for the electronic dynamics in DMAde with the pipi*(L(a)), pipi*(L(b)), and npi* states similar to those in Ade and an intramolecular charge-transfer (ICT) state, which has no counterpart in Ade, responsible for the long-wavelength fluorescence.

Citation

Nina K Schwalb, Friedrich Temps. A modified four-state model for the "dual fluorescence" of N(6),N(6)-dimethyladenine derived from femtosecond fluorescence spectroscopy. The journal of physical chemistry. A. 2009 Nov 26;113(47):13113-23

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PMID: 19569655

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